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Process for the preparation of fullerene derivatives

Foreign code F110003955
File No. E07902WO
Posted date Jul 7, 2011
Country EPO
Application number 07739375
Gazette No. 2006276
Date of filing Mar 15, 2007
Gazette Date Dec 24, 2008
International application number JP2007055933
International publication number WO2007111226
Date of international filing Mar 15, 2007
Date of international publication Oct 4, 2007
Priority data
  • P2006-081836 (Mar 24, 2006) JP
  • 2007JP55933 (Mar 15, 2007) WO
Title Process for the preparation of fullerene derivatives
Abstract The present invention provides a method for producing a fullerene derivative comprising reacting: a fullerene; an organometallic reagent (A) comprising B, Al, Zn, Sn, Pb, Te, Ti, Mn, Zr or Sm; and a copper compound (B).
Outline of related art and contending technology BACKGROUND ART
Since the method for synthesizing a carbon cluster (hereinafter also referred to as "fullerene"), in which carbon atoms are arranged to form a spherical shape or a rugby ball shape, was established, fullerene has been energetically studied.As a result, many fullerene derivatives have been synthesized.
With respect to specific examples of such fullerene derivatives, methods for synthesizing a fullerene derivative, in which 5 organic groups bind to a fullerene skeleton (hereinafter also just referred to as "penta(organo)fullerene derivative"), have been reported (e.g., Japanese Laid-Open Patent Publication No. Hei 10-167994; Japanese Laid-Open Patent Publication No. Hei 11-255509; J. Am. Chem. Soc., 118, 12850 (1996); Org. Lett., 2, 1919 (2000); and Chem. Lett., 1098 (2000)).
As a method for producing a penta(organo)fullerene derivative, for example, it is known that, by reacting an organocopper reagent prepared using a phenyl Grignard reagent and CuBr·S(CH3)2 with fullerene C60, a phenylated fullerene derivative, in which phenyl groups constituting the phenyl Grignard reagent are regioselectively added to surround one 5-membered ring of fullerene C60 (C60Ph5H), can be quantitatively obtained (e.g., Japanese Laid-Open Patent Publication No. 10-167994).
However, since compounds having a substituent such as a carboxyl group and an ester group are active against Grignard reagents, it is difficult to prepare Grignard reagents having such a substituent.Therefore, it has been impossible to use methods for conveniently synthesizing a fullerene derivative having a substituent such as a carboxyl group and an ester group using a Grignard reagent having such a substituent.
As a result, in order to synthesize a fullerene derivative having such a substituent, it has been necessary to use time-consuming methods such as: methods for producing a penta(organo)fullerene derivative by reacting a large excess of bromomalonate derivative with fullerene in a multistage manner (Angew. Chem. Int. Ed. Engl., 33, 2339 (1994); Angew. Chem. Int. Ed. Engl., 34, 1607 (1995); etc.); and a multistage synthesis method comprising the step of reacting C60I6 with benzene to cause electrophilic substitution (J. Chem. Soc., Chem. Commun. 1464 (1994)); etc.In addition, in the case of these methods for producing fullerene derivatives, there are problems that it is very difficult to regioselectively obtain a penta(organo)fullerene derivative, and that the yield of fullerene derivative is low.
Scope of claims [claim1]
1. A method for producing a fullerene derivative comprising reacting:
a fullerene;
an organometallic reagent (A) comprising: a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryalkyl group or a substituted or unsubstituted aryl group; and B, Al, Zn, Sn, Pb, Te, Ti, Mn, Zr or Sm; and
a copper compound (B).
[claim2]
2. A method for producing a fullerene derivative comprising reacting:
a fullerene;
an organometallic reagent (A) comprising: a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryalkyl group or a substituted or unsubstituted aryl group; and Al, Zn, Sn or Pb; and
a copper compound (B).
[claim3]
3. A method for producing a fullerene derivative comprising reacting:
a C60 fullerene;
an organometallic reagent (A) comprising: an alkyl group which may have one or more substituents selected from the group consisting of an ester group, an amide group, a cyano group and a halogen atom, an alkenyl group which may have one or more substituents selected from the group consisting of an ester group, an amide group, a cyano group and a halogen atom, or an aryl group which may have one or more substituents selected from the group consisting of an ester group, an amide group, a cyano group and a halogen atom; and Zn; and
a monovalent or divalent copper compound (B).
[claim4]
4. The method for producing a fullerene derivative according to any one of claims 1 to 3, wherein the fullerene derivative is represented by the following formula (1):
        Cn(R4) m(R5) p     (1)
wherein n is an even number of 60 or more; m is an integer from 3 to 10; p is 1 or 2; each R4 is independently a hydrogen atom, a substituted or unsubstituted C1 - C20 hydrocarbon group, a substituted or unsubstituted C1 - C20 alkoxy group, a substituted or unsubstituted C6 - C20 aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkylthio group (-SY1: in the formula, Y1 is a substituted or unsubstituted C1 - C20 alkyl group), a substituted or unsubstituted arylthio group (-SY2: in the formula, Y2 is a substituted or unsubstituted C6 - C18 aryl group), a substituted or unsubstituted alkylsulfonyl group (-SO2Y3: in the formula, Y3 is a substituted or unsubstituted C1 - C20 alkyl group), or a substituted or unsubstituted arylsulfonyl group (-SO2Y4: in the formula, Y4 is a substituted or unsubstituted C6 - C18 aryl group); and R5 is a hydrogen atom or a C1 - C20 hydrocarbon group.
[claim5]
5. The method for producing a fullerene derivative according to any one of claims 1 to 3, wherein the fullerene derivative is a fullerene derivative C60(R4)5R5 represented by the following formula (2):wherein each R4 is independently a hydrogen atom, a substituted or unsubstituted C1 - C20 hydrocarbon group, a substituted or unsubstituted C1 - C20 alkoxy group, a substituted or unsubstituted C6 - C20 aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkylthio group (-SY1: in the formula, Y1 is a substituted or unsubstituted C1 - C20 alkyl group), a substituted or unsubstituted arylthio group (-SY2: in the formula, Y2 is a substituted or unsubstituted C6 - C18 aryl group), a substituted or unsubstituted alkylsulfonyl group (-SO2Y3: in the formula, Y3 is a substituted or unsubstituted C1 - C20 alkyl group), or a substituted or unsubstituted arylsulfonyl group (-SO2Y4: in the formula, Y4 is a substituted or unsubstituted C6 - C18 aryl group); and R5 is a hydrogen atom or a C1 - C20 hydrocarbon group.
[claim6]
6. The method for producing a fullerene derivative according to claim 4 or 5, wherein R4 has one or more substituents selected from the group consisting of an ester group, a carboxyl group, an amide group, an alkyne group, a trimethylsilyl group, a trimethylsilylethynyl group, an aryl group, an amino group, a phosphonyl group, a thio group, a carbonyl group, a nitro group, a sulfo group, an imino group, a halogeno group, and an alkoxy group.
[claim7]
7. The method for producing a fullerene derivative according to claim 4 or 5, wherein R4 has one or more substituents selected from the group consisting of an ester group, an amide group, an alkyne group, a trimethylsilyl group, a trimethylsilylethynyl group, and an aryl group.
[claim8]
8. The method for producing a fullerene derivative according to any one of claims 4 to 7, wherein R5 is a hydrogen atom or a C1 - C20 alkyl group.
[claim9]
9. The method for producing a fullerene derivative according to any one of claims 1 to 3, wherein the fullerene derivative is represented by the following formula (3):wherein R5 is a hydrogen atom or a substituted or unsubstituted C1 - C20 hydrocarbon group; and each R6 is independently a hydrogen atom or a substituted or unsubstituted C1 - C20 hydrocarbon group.
[claim10]
10. The method for producing a fullerene derivative according to claim 9, wherein R5 is a hydrogen atom or a substituted or unsubstituted C1 - C20 alkyl group.
[claim11]
11. The method for producing a fullerene derivative according to claim 9 or 10, wherein R6 is a hydrogen atom, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, or a substituted or unsubstituted C2 - C20 alkynyl group.
[claim12]
12. The method for producing a fullerene derivative according to any one of claims 1 to 11, wherein an organic group included in the organometallic reagent (A) is a methyl group, an ethyl group, an isopropyl group, a butyl group or a phenyl group.
[claim13]
13. The method for producing a fullerene derivative according to any one of claims 1 to 12, wherein the copper compound (B) is CuBr·S(CH3)2.
[claim14]
14. A fullerene derivative represented by the following formula (3):wherein R5 is a hydrogen atom or a substituted or unsubstituted C1 - C20 hydrocarbon group; and each R6 is independently a hydrogen atom or a substituted or unsubstituted C1 - C20 hydrocarbon group.
[claim15]
15. The fullerene derivative according to claim 14, wherein R5 is a hydrogen atom or a substituted or unsubstituted C1 - C20 alkyl group.
[claim16]
16. The fullerene derivative according to claim 14 or 15, wherein R6 is a hydrogen atom, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, or a substituted or unsubstituted C2 - C20 alkynyl group.
[claim17]
17. A fullerene derivative represented by the following formula (4):wherein each R6 is independently a hydrogen atom or a substituted or unsubstituted C1 - C20 hydrocarbon group; M is a metallic atom; L is a ligand of M; and n is the number of Ls.
[claim18]
18. The fullerene derivative according to claim 17, wherein R6 is a hydrogen atom, a substituted or unsubstituted C1 - C20 alkyl group, a substituted or unsubstituted C2 - C20 alkenyl group, or a substituted or unsubstituted C2 - C20 alkynyl group.
[claim19]
19. The fullerene derivative according to claim 17 or 18, wherein M is a transition metal.
[claim20]
20. The fullerene derivative according to claim 17 or 18, wherein M is a group 8-10 transition metal.
[claim21]
21. The fullerene derivative according to claim 17 or 18, wherein: M is Fe, Ru, or Os; n is an integer from 0 to 5; and L is a halogen atom, alkoxy group, alkyl group, alkyne group or cyclopentadienyl group.
  • Applicant
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • Inventor
  • NAKAMURA, Eiichi
  • MATSUO, Yutaka
  • NAKAE, Takahiro
IPC(International Patent Classification)
Specified countries Contracting States: DE
Reference ( R and D project ) ERATO NAKAMURA Functional Carbon Cluster AREA
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